Sulfur-containing esters of substituted hydroxyphenyl alkanoic acids

ABSTRACT

Compounds are prepared having one of the following formulae: i A. HOR1CH2S(CH2)nCOOR4   c. HOR1CmH2m-1(S(CH2)nCOOR3)2 d. (HOR1CH2)2C(COOR2)2 e. HOR1CH2O(CH2)nCOOR2 f. HOR1CH2OCH2CH2OOCCH2CH2S(CH2)nCOOR3 g. HOR1CH2CH(COOR2)2   where R5 and R6 are hydrogen, alkyl, cycloaklyl, aryl or aralkyl, the total carbon atoms in R5 and R6 is between four and 36 carbon atoms, is preferably not over 12 carbon atoms and R6 is preferably in the ortho position, R2 is   R3 is hydrocarbyl, preferably alkyl or alkenyl, e.g., of one to 18 carbon atoms, n is 1 or 2, R14 is H or COOR2, m is 1, 2, 3 or 4, y is 0 or 1, and R4 is either R2 or R3 and R15 is hydrogen or lower alkyl. The above compounds are useful as antioxidants.

United States Patent Hechenbleikner et a1.

1*Jan. 29, 1974 SULFUR-CONTAINING ESTERS OF SUBSTITUTED HYDROXYPHENYLALKANOIC ACIDS [75] Inventors: Ingenuin A. Hechenbleikner,

Kenwood; John F. Hussar, Loveland; Arthur F. Koeniger, Cincinnati;Robert E. Bresser, Sharonville, all of Ohio [73] Assignee: CincinnatiMilacron Chemicals Inc.,

Reading, Ohio 1 Notice: The portion of the term of this patentsubsequent to Oct. 2, 1990, has been disclaimed.

[22] Filed: Mar. 14, 1972 [21] Appl. No.: 234,649

Related US. Application Data [62] Division of Ser. No. 884,016, Dec. 10,1969, Pat. No.

OTHER PUBLICATIONS Eggensferger et al. CA. 71 13810e (1969).

Primary Examiner-Lorraine A. Weinberger Assistant ExaminerJohn F.Terapane Attorney, Agent, or Firm-Cushman, Darby & Cushman [57] ABSTRACTCompounds are prepared having one of the following formulae:

a. HOR,CH S(CI-I ),,COOR

HOB (EH y ICOORi l m 2m-1( 2)n 3)2 d. (HOR CH C(COOR e. HOR CH O(CH),,COOR

f. HOR CH OCH CH OOCCH CH S(CH ),,COOR g. uomcmcmcoom (h) COOR:

HOR1CH=C where HOR is where R and R are hydrogen, alkyl, cycloaklyl,aryl or aralkyl, the total carbon atoms in R and R is between four and36 carbon atoms, is preferably not over 12 carbon atoms and R ispreferably in the ortho position, R is R is hydrocarbyl, preferablyalkyl or alkenyl, e.g., of one to 18 carbon atoms, n is 1 or 2, R is Hor COOR m is 1, 2, 3 or 4, y is 0 or 1, and R is either R or R and R ishydrogen or lower alkyl. The above compounds are useful as antioxidants.

2 Claims, No Drawings SULFUR-CONTAINING ESTERS OF SUBSTITUTEDHYDROXYPHENYL ALKANOIC ACIDS This is a division of application Ser. No.884,016 filed Dec. 10, 1969, now US Pat. No. 3,699,152.

The present invention relates to the preparation of novel phenolicantioxidants.

The compounds of the invention have one of the following formulae:

where R, and R are hydrogen, alkyl, cycloalkyl, aryl or aralkyl, thetotal carbon atoms in R and R is between four and 36, is preferably notover 12 carbon atoms and R is preferably in the ortho position, R isCHQ(C H2B)S o Hg -r C0033, cmsmnnno 0 0R:

cmoaswrmno 0 CR3, or

CH2 (CHgOCHgCHgS(CHz) C 0 Q1592 R is hydrocarbyl preferably alkyl oralkenyl, e.g., of one to 18 carbon atoms, R is hydrogen or COOR R ishydrogen or lower alkyl, n is 1 or 2, m is l, 2, 3 or 4, y is O or 1,and R is either R or R The general procedure for making the compounds ofthe present invention is somewhat similar to that in Geigy Belgian Pat.No. 710,873 and Goodrich French Pat. No. 1,536,020 (Dutch applicationNo. 6712339).

As starting reactants there can be used hindered phenols such as 2,6di-t-butylphenol and other phenols having the formula including but notlimited to those set forth in Table l.

TABLE 1 Compound R, R

1 t-butyl -t-butyl 2 t-butyl H 3 t-butyl S-l-butyl 4 octadecyl6-octadecyl 5 methyl fi-propyl 6 t-amyl 6-ethyl 7 isooctyl S-methyl 8isooctyl H 9 isopropyl 6-isopropyl l0 sec. butyl 5-sec. butyl l l sec.butyl 3-sec. butyl l2 sec. butyl 6-sec. butyl l3 butyl 6-butyl l4 octyl5-octyl l5 t-butyl 6-methyl l6 t-butyl S-octaclecyl l7 cyclohexyl 6ethyl l8 benzyl 6-benzyl l9 octadecyl H 20 octadecyl 6methyl 21cyclododecyl 6-methyl 22 nonyl 6-nonyl Other hindered phenol startingmaterials are 3,5-di-tbutyl-4-hydroxybenzyl chloride and other phenolshaving the formula Its JJlIzCl including but not limited to those setforth in Table 2.

TABLE 2 Compound R R la t-butyl 6-t-butyl 2a t butyl H 3a t-butylS-t-butyl 4a octadecyl 6-octadecyl 5a methyl 6-propyl 6a t-amyl 6-ethyl7a isooctyl S-methyl 8a isooctyl H 9a isopropyl 6-isopropyl lOa sec.butyl 5-sec. butyl I la sec. butyl 3-sec. butyl 12a sec. butyl 6-sec.butyl 13a butyl 6-butyl l4a octyl S-octyl l5a t-butyl 6'methyl 16at-butyl 5 -octadecyl 17a cyclohexyl 6-ethyl 18a benzyl 6-benzyl 19aoctadecyl H 200 octadecyl 6-methyl 2 la cyclododecyl methyl 22a nonyl6-nonyl Additional starting materials are made by reacting a hinderedphenol such as in Table l with an ethylenically unsaturated compound inthe presence of a condensing agent, e.g., anhydrous AlCl or BF Asethylenically unsaturated compounds there can be used acrylic acid,methacrylic acid, methyl vinyl ketone, butyl vinyl ketone, methylmethacrylate, ethyl acrylate, methyl acrylate, methyl allyl ketone,maleic acid, itaconic acid, vinyl esters, e.g., vinyl acetate, vinylbutyrate, vinyl propionate, vinyl ethers, e.g., methyl vinyl ether,butyl vinyl ether, maleic acid and the like. Such intermediates have theformula l R: Rs

III

R is H, COOH or lower alkyl, R

is H, lower alkyl or CH COOH, R is OH or lower alkyl.

For example 2,6-di-t-butyl phenol and acrylic acid in the presence ofAlCl gave 3-(3,5-di-t-butyl-4- hydroxyphenyl)'propionic acid. In placeof 2,6-di-tbutylphenol there can be used any of the phenols in Table lto give the corresponding 3-substituted propionic acids. Similarlyreplacing the acrylic acid by methacrylic acid gave3-(3,5-di-t-butyl-4-hydroxyphenyl)-2- methyl propionic acid or byethacrylic acid gave 3- (3 ,5 -di-t-butyl-4-hydroxyphenyl )-2-ethylpropionic acid, or by cro'tonic acid gave 3-(3,5-di-t-butyl-4-hydroxyphenyl)-3-methyl propionic acid.

The starting compounds can also be prepared by the method of US. Pat.No. 3,247,240 in which the hindered phenol is reacted with anappropriate vinyl compound in the presence of a basic catalyst such assodium t-butoxide or sodium methylate. For example there were added to169.5 parts of 2,6-di-t-butyl phenol, 4.9 parts of sodium methylateunder a nitrogen atmosphere. Then 78.8 parts of methyl acrylate wereadded over a period of minutes. When the exothermic reaction hadsubsided the mixture was heated at 60 C. for 3 hours andmethyl-3-(3,5-di-t-butyl-4- hydroxyphenyl) propionate isolated, M.P.6364.5 C. after recrystallization. Methyl vinyl ketone with2,6-dit-butyl phenol using AlCl as a condensing agent gave 1-( 3 ,5-di-t-butyl-4-hydroxyphenyl)-3-butanone. In place of 2,6-di-t-butylphenol there can be used any of the phenols in Table 1 to give thecorresponding 1- substituted 3-butanones. Similarly replacing the methylvinyl ketone by ethyl vinyl ketone gave l-(3,5-di-tbutyl-4-hydroxyphenyl)-3-pentanone, or by methyl vinyl ketone gavel-(3,5-di-t-butyl-4-hydroxyphenyl)- 2-methyl-3-butanone. Maleic acidwith 2,6-di-t-butyl phenol using AlCl as a condensing agent gave(Ii-(3,5- di-t-butyl-4-hydroxyphenyl) succinic acid. In place of2,6-di-t-butyl phenol there can be used any of the phenols in Table 1 togive the corresponding a-substituted succinic acids. Similarly replacingthe maleic acid by itaconic acid gave a-(3,5-di-t-butyl-4-hydroxybenzyl)succinic acid.

Any of the free acids can be reacted to form the corresponding allylesters in the presence of a mineral acid, e.g., hydrochloric acid orsulfuric acid or a strong organic acid such as p-toluene sulfonic acidwith or without an appropriate inert hydrocarbon such as benzene,toluene or heptane to remove the water of reaction. Thus, there can beprepared ally] 3-(3,5-di-tbutyl-4-hydroxyphenyl) propionate as well asthe corresponding allyl 3-substituted propionates of any of the otherphenols in Table 1; the diallyl l-(3,5-di-t-butyl-4- hydroxyphenyl)succinate as well as the corresponding diallyl l-substituted succinatesof any of the other phenols in example 1.

As intermediates for reacting with 3,5-di-t-butyl-4- hydroxybenzylchloride (or the corresponding benzyl,

N,N-dialkyl amine) or the other benzyl chlorides of Table 2 there can beused the addition products of diallyl malonate with hydrocarbyl,preferably alkyl or alkenyl mercaptopropionates or mercaptoacetates suchas methyl mercaptopropionate, butyl mercaptopropionate, octylmercaptopropionate, isooctyl mercaptopropionate, stearylmercaptopropionate, oleyl mercaptopropionate, cyclohexylmercaptopropionate, lauryl mercaptopropionate, methyl mercaptoacetate,ethyl mercaptoacetate, butyl mercaptoacetate, amyl mercaptoacetate,hexyl mercaptoacetate, decyl mercaptoacetate, cetyl mercaptoacetate,lauryl mercaptoacetate, linoleyl mercaptopropionate, linolenylmercaptopropionate, phenyl mercaptopropionate, p-tolyl mercaptoacetate,phenyl mercaptoacetate, o-tolyl mercaptopropionate, benzylmercaptoacetate, benzyl mercaptopropionate.

For making compounds where R is there can be used as intermediatesdihydrocarbyl, preferably dialkyl or dialkenyl, dithiodipropionates anddithiodiacetates such as dilauryl dithiodipropionate, dilauryldithiodiacetate, dimethyl dithiodipropionate, diethyl dithiodiacetate,dioctadecyl dithiodipropionate, dioctadecyl dithiodiacetate, dioleyldithiodipropionate, dioleyl dithiodiacetate, diphenyldithiodipropionate, dibenzyl dithiodiacetate.

The compounds of the invention within formula (a) are prepared byreacting a compound having the formula l-IOR Cl-I SH with a compoundhaving the formula CH =CHCOOR or by reacting a compound having theformula HOR CH SCH CH COOCH CH=CH with a compound having the formula ROOC(CH ),,Sl-I.

The compounds of the invention within Formula (b) can be preparedreacting a compound having the formula with a compound having theformula R OOC(CI-I ),,SH or by reacting a compound having the formula R7ft RK JHCHC O O CHzCH=CHz when R, and R are both hydrogen with acompound having the formula R OOC(CH ),,SI-I.

The compounds of the invention within formula (c) can be prepared byreacting a compound having the formula where R is lower alkyl with acompound having the formula R OOC(CH ),,SH or by reacting a compoundhaving the formula HOR,CHO with a compound having the formula R;,OOC(CH),,SH.

The compounds of the invention within formula (d) are prepared byreacting a compound having the formula o o 0 om-o 11:01-17 with acompound having the formula R;,OOC(CH,),,SH. The compound having theformula COO CHzCH=CH2 can be prepared by the procedure of Belgian Pat.No. 710,873, e.g., example 1 or French Pat. No. 1,536,020 example 1replacing the diethyl malonate by diallyl malonate. Alternatively thelower alkyl products of the Belgian or French patent, e.g., diethyl2,2-bis(3',5-dit-butyl-4'-hydroxybenzyl)-malonate can be transesterifiedwith allyl alcohol to form the diallyl ester.

The compounds of the invention within formula (e) are prepared byreacting a compound having the formula HOR CH Cl with allyl glycolate orallyl hydroxypropionate and then with a hydrocarbyl mercaptoacetate ormercaptopropionate The compounds of the invention within formula (f) canbe prepared by reacting a compound having the formula HOR CH CI withhydroxyethyl acrylate and then with a hydrocarbyl mercaptoacetate ormercaptopropionate.

The compounds of the invention within formula (g) can be prepared byreacting a compound having the formula l-loR CH Cl or Rn HO iCH2N whereR and R are alkyl with a compound having the formula COORJ COORz Thecompounds of the invention within formula (h) are prepared by reacting acompound having the formula HOR CHO with a compound having the formulaCOORz COOR:

Representative of compounds within formula (a) are 3,5-di-t-butyl-4-hydroxybenzylallylcarboxyethyl sulfide (also calledallyl-3-(3,5-di-t-butyl-4-hydroxybenzylthio propionate) and prepared byreacting 3,5-di-t-butyl-4- hydroxybenzyl mercaptan with allyl acrylate(or with acrylic acid followed by esterification with allyl alcohol) orthe corresponding analogues prepared by replacing the3,5-di-t-butyl-4-hydroxybenzyl mercaptan with a mercaptan of the formulaIllustrative of such mercaptans are those set forth in Table 3.

TABLE 3 Compound R R 1 t-hutyl 6-t-butyl 2 t-butyl H 3 t-hulyl S-t-hutyl4 octadecyl fi-ucludccyl 5 methyl (v-pmpyl 6 t-amyl fi-ethyl 7 isooctylS-methyl 8 isooctyl H 9 isopropyl fi-isopropyl 10 sec. butyl 5sec. butyll 1 sec. butyl 3-secv butyl 12 sec. butyl 6-sec. butyl l3 butyl 6-butyll4 octyl 5-octyl l5 t-butyl 6-methyl l6 t-butyl S-oetadecyl l7cyclohexyl 6-ethyl l8 benzyl 6benzyl l9 octadecyl H 20 octadecyl6-methyl 21 cyclododecyl 6-methyl 22 nonyl 6-nonyl Also within formula(a) are 3,5-di-t-butyl-4- hydroxybenzyl lauryl carboxyethyl sulfide(prepared by reacting 3,5-di-t-butyl-4 hydroxybenzyl mercaptan withlauryl acrylate) or the corresponding analogues prepared by replacingthe 3,5-di-t-butyl-4 hydroxybenzyl mercaptan with each of the mercaptansin Table 3. Also within formula (a) are the compounds made replacinglauryl acrylate with other hydrocarbyl acrylates, e.g., methyl acrylate,octadecyl acrylate, oleyl acrylate, benzyl acrylate, phenyl acrylate,p-tolyl acrylate, cyclohexyl acrylate, isooctyl acrylate, 2-ethyl hexylacrylate with 3,5-di-t-butyl-4-hydroxybenzyl mercaptan.

Furthermore within formula (a) is 3-(butoxycarboethylthio) propyl-3 3,5-di-t-butyl-4- hydroxybenzylthio) propionate made from allyl-3-(3,5-di-t-butyl 4-hydroxybenzylthio) propionate and butyl mercaptopropionateas well as the corresponding analogues made by replacing butylmercaptopropionate by any of the hydrocarbyl mercaptoacetates ormercaptopropionates set forth previously (i.e., those mentioned assuitable for reacting with diallyl malonate). Additionally withinformula (a) are the compounds prepared by reacting butylmercaptopropionate with any of the analogues ofallyl-3-(3,5-di-t-butyl-4- hydroxybenzylthio) propionate set forthsupra.

Within formula (b) are 2,3-bis(dodecoxycarboethylthio)propyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate and thecorresponding compounds made by re placing the dilauryldithiodipropionate in example 6 with any of the dihydrocarbyldithiodipropionates or dithiodiacetates set forth previously as well asthe compounds prepared by reacting dilauryl dithiodipropionate with anyof the analogues of allyl-3-(3,5-di-t-butyl- 4-hydroxybenzylthio)propionate set forth supra.

Also within formula (b) are 2,2-bis[3-(dodecoxycarboethylthio)propoxymethyl] butyl-3-(3,5-di-t-butyl-4- hydroxyphenyl) propionate andits analogues prepared by replacing the lauryl mercaptopropionate inexample 7 with any of the other hydrocarbyl mercapto acetates andpropionates set forth supra as well as the compounds made by reactinglauryl mercaptopropionate with compounds of the type2,2-bis(allyloxymethyl) butyl-3'-(3,5-di-t-butyl-4-hydroxyphenyl)propionate but having the 3,S-di-t-butyl-4-hydroxyphenyl group replacedby the corresponding group of any of the phenols set forth in Table 1.

Additionally within formula (b) are bis[3- (dodecyloxycarboethylthio)propyl -a-( 3 ,S-di-t-butyli -hydroxyphenyl) succinate and its analoguesprepared by replacing the lauryl mercaptopropionate in example 1 l withany of the other hydrocarbyl mercapto acetates and mercaptopropionatesset forth supra as well as the compounds made by reacting laurylmercaptopropionate with compounds of the typediallyl-a-(3,5-di-tbutyl-4-hydroxyphenyl) succinate but having the 3,5-di-t-butyl4-hydroxyphenyl group replaced by the corresponding group ofany of the phenols set forth in Table 1.

Furthermore within formula (b) are dodecyloxycarboethylthiopropyl(3,5-di-t-butyl-4-hydroxyphenyl) propionate and its analogues preparedby replacing the lauryl mercaptopropionate in example 12 with any of theother hydrocarbyl mercaptoacetates and mercaptopropionates set forthsupra as well as any of the compounds made by reacting laurylmercaptopropionate with compounds of the typeallyl-,B-(3,5-di-t-butyl-4- hydroxyphenyl) propionate but having the3,5-di-tbutyl-4-hydroxyphenyl group replaced by the corresponding groupof any of the phenols set forth in Table Within formula (c) arel-(3,5-di-t-butyl-4- hydroxyphenyl)-3,3-bis(dodecoxycarboethylthio)butane and its analogues prepared by replacing the laurylmercaptopropionate in example 2 with any of the other hydrocarbylmercaptoacetates and mercaptopropionates set forth supra as well as anyof the compounds made by reacting lauryl mercaptopropionate withcompounds of the type w1-(3,5-di-t-butyl-4-hydroxyphenyl)-3-butanone buthaving the 3,5-di-t-butyl-4- hydroxyphenyl group replaced by thecorresponding group of any of the'phenols in Table 1 supra or byreacting lauryl mercaptopropionate withl-(3,5-di-tbutyl-4-hydroxyphenyl)-3-pentanone orl-(3,5-di-tbutyl-4-hydroxyphenyl)-2-methyl-3-butanone or other compoundsof formula III.

Also within formula (c) arebis(carbodecoxyethylthio)-4-hydroxy-3,S-di-t-butylphenyl methane and itsanalogues prepared by replacing the lauryl mercaptopropionate in example13 with any of the other hydrocarbyl mercaptoacetates andmercaptopropionates set forth supra as well as any of the compounds madeby reacting lauryl mercaptopropionate with compounds of the type3,5-di-t-butyl-4- hydroxybenzaldehyde but having the 3,5-di-t-butyl-4-hydroxyphenyl group replaced by the corresponding group of any of thephenols in Table 1 supra.

Within formula ((1) are bis(3,5-di-t-butyl-4- hydroxybenzyl)bis(butoxycarboethylthiopropyl) ma- Within formula (e) are3,5-di-t-butyl-4-hydroxybenzylbutyl carboxyethylthiopropylcarboxymethylether and its analogues prepared by replacing the butylmercaptopropionate in example 16 with any of the other hydrocarbylmercaptoacetates and mercaptopropionates set forth supra as well as anyof the compounds made by replacing the 4-hydroxy-3,5-di-t-butyl hydroxybenzyl chloride in example 16 with any of the substituted benzylchlorides in Table 2.

Within formula (f) are 3 ,5-di-t-butyl-4- hydroxybenzyllaurylcarboxyethylthioethylcarboxyethyl ether and its analogues preparedby replacing the lauryl mercaptopropionate in example 18 with any of theother hydrocarbyl mercaptoacetates and mercaptopropionates set forthsupra as well as any of the compounds made by replacing the4-hydroxy-3,5- di-t-butyl-4-hydroxybenzyl chloride in example 1 8 withany of the substituted benzyl chlorides in Table 2.

Within formula (g) are 2,6-di-t-butyl-4-[ethylene bis-(butyl-3-thiopropoxycarbopropionate)] phenol and the correspondingproducts made by reacting N,N- dimethyl-3,5-di-t-butyl-4-hydroxybenzylamine with the addition product of any hydrocarbyl mercaptoacetate ormercaptopropionate set forth supra with diallyl malonate. Also withinformula (g) are the reaction products of methylene bis(butyl-3-thiopropoxycarbopropionate) with any of the substituted benzylchlorides in Table 2.

Within formula (h) are 3,5-di-t-butyl-4- hydroxybenzal methylenebis(methyl-2-methyl-3- thioethoxycarbopropionate) and its analoguesprepared by replacing methylene bis(methyl-2-methyl-3-thioethoxycarbopropionate) by other esters in which the esterifyinggroup instead of methyl is isooctyl, d0- decyl, octadecyl, cyclohexyl,benzyl, phenyl or p-tolyl for example. The methylenebis(methyl-2-methyl-3- thioethoxycarbopropionate) can be prepared by theaddition of methyl methacrylate to bis(2-mercaptoethyl) malonate.

Also within formula (h) are the reaction products of methylenebis(methyl-2-methyl-3-thioethoxycarb0propionate) with compounds of thetype 3,5-di-t-butyl-4- hydroxybenzaldehyde but having the3,5-di-t-butyl-4- hydroxyphenyl group replaced by the correspondinggroup of any of the phenols in Table 1 supra. In making the compounds ofgroup (h) in place of using hydrocarbyl methacrylates there can be usedhydrocarbyl acrylates for addition to the bis(2-mercaptoethyl) malonate.

Unless otherwise indicated all parts and percentages are by weight.

The compounds of the present invention are primarily useful asantioxidants and stabilizers for hydrocarbon resins but are also usefulwith any resin requiring stabilization against atmospheric exposure.Thus, they can also be used with halogen containing resins.

As the halogen containing resins there can be used resins made fromvinylidene compounds such as vinyl chloride, vinylidene chloride, vinylchloroacetate, chlorostyrenes, vinyl bromide and chlorobutadienes.

Such vinylidene compounds may be polymerized alone or in admixture witheach other or with other vinylidene compounds. Thus, vinyl chloride canbe copolymerized with vinyl esters of carboxylic acids, e.g., vinylacetate and vinyl butyrate esters of unsaturated acids, e.g., acrylatessuch as methyl acrylate, ethyl acrylate, butyl acrylate and allylacrylate as well as the corresponding methacrylates, e.g., methylmethacrylate and butyl methacrylate, vinyl aromatic compounds,

9 e.g., styrene, divinyl benzene, a-methyl styrene, pmethyl styrene,dienes such as butadiene and isoprene, unsaturated amides such asacrylamide, methacrylamide and the esters of kfi-unsaturated carboxylicacids. Specific examples of such esters are diethyl maleate, dibutylmaleate and dibutyl fumarate.

The stabilizers of the present invention are also effective whenintimately mixed with halogen containing resins in which part or all ofthe halogen is introduced into a preformed resin, e.g., chlorinatedpolyethylene, and rubber hydrochloride.

Typical examples of copolymers include vinyl chloride-vinyl acetate(95:5 weight ratio), vinyl chloridevinyl acetate (87: 1 3 weight ratio),vinyl chloride-vinyl acetate maleic anhydride (86:13:1 weight ratio),vinyl chloride-vinylidene chloride (95:5 weight ratio), vinylchloride-diethyl fumarate (95:5 weight ratio), vinylchloride-trichloroethylene (95:5 weight ratio).

The resin, e.g., polyvinyl chloride, can either be plasticized orunplasticized. As the plasticizer there can be employed conventionalmaterials sucb as dioctyl phthalate. The plasticizer is used inconventional amount, e.g., 10 to 100 parts for each 100 parts of thevinyl chloride containing resin.

The mercapto containing stabilizers of the present invention are used inan amount of 0.05 to 20 parts, preferably 0.1 to 10 parts per 100 partsof halogen containing resin.

There can also be incorporated 0.1 to 10 parts per 100 parts of thehalogen containing resin conventional metal salt stabilizers. Thus,there can be used barium, strontium. calcium, cadmium, zinc, lead, tin,magnesium, cobalt, nickel, titanium and aluminum salts of phenols,aromatic carboxylic acids, fatty acids and epoxy fatty acids.

Also there can be incorporated a phosphite, e.g., an alkyl, aryl oraralkyl phosphite in an amount of 0.1 to 10 parts per 100 parts ofresin. Typical of such phosphites are triphenyl phosphite, tris decylphosphite, decyl diphenyl phosphite, di(p-tert. butylphenyl) phenylphosphite, diphenyl o-cresyl phosphite, trioctyl phosphite, tricresylphosphite and tribenzyl phosphite.

The compounds of the present invention are also stabilizers formonoolefin polymers such as polyethylene, polypropylene, ethylenepropylene copolymers (e.g., 50:50 80:20 and 20:80), ethylene-monoolefincopolymers wherein the monoolefin has four to 10 carbon atoms and ispresent in a minor amount, e.g., ethylenebutene-l copolymer (95:5) andethylene-decene-l copolymer (90:10). Furthermore, they can be used tostabilize natural rubber, styrene-butadiene rubber (SBR rubber), e.g.,(75 percent butadiene, 25 percent styrene) and EPDM rubbers andacrylonitrile-butadiene styrene terpolymers (ABS).

As the EPDM rubber there can be employed many of the commerciallyavailable EPDM rubbers. The EPDM rubber normally contains 30 to 70 molarpercent (preferably 50 to 60 molar percent) of ethylene, 65 to 20 molarpercent (preferably 35 to 45 molar percent propylene) and 1 to 15 molarpercent (preferably 3 to 5 molar percent) of the nonconjugatedpolyolefin. Usually the polyolefin is not over molar percent. Theethylene and propylene can each be 5 to 95 molar percent of thecomposition.

As used in the present specification and claims the term nonconjugatedpolyolefin includes aliphatic unconjugated polyene hydrocarbons andcycloaliphatic nonconjugated polyene hydrocarbons, e.g., endocyclicdienes. Specific examples of suitable nonconjugated polyolefins includepentadiene-l ,4; hexadiene-l,4; dicyclopentadiene, methylcyclopentadiene dimer, cyclododecatriene, cyclooctadiene-l,5;5-methylene-2- norbomene.

Specific examples of suitable terpolymers are the Royalenes whichcontain 55 mole percent ethylene, 40 to 42 mole percent propylene and 3to 5 mole percent dicyclopentadiene; Enjay terpolymers, e.g., ERP-404 ofEnjay and Enjay 3509 which contains about 55 mole percent ethylene, 41mole percent propylene and 4 mole percent 5-methylene-2-norborr ene;Nordel, a terpolymer of 55 mole percent ethylene, 40 mole percentpropylene and 5 mole percent hexadiene-l ,4. Another suitable terpolymeris the one containing 50 mole percent ethylene, 47 mole percentpropylene and 3 mole percent 1,5-cyclooctadiene (Dutrel).

Examples of EPDM rubbers are given in U.S. Pat. Nos. 2,933,480;3,000,866; 3,063,973; 3,093,620; 3,093,621, and 3,136,739, in BritishPat. No. 880,904 and in Belgian Pat. No. 623,698.

Terpolymers and other EPDM rubbers from ethylene, propylene anddicyclopentadiene are exemplified in Tarney U.S. Pat. No. 3,000,866;Adamck U.S. Pat. No. 3,136,739 and Dunlop (British) Pat. No. 880,904.EPDM rubbers from ethylene, propylene and 1,4- hexadiene are exemplifiedin Gresham U.S. Pat. No. 2,933,480. As in Gresham other suitablenonconjugated diolefins are 1,4-pentadiene; 2-methy1-1,5 hexadiene,3,3-dimethyl-1, 5-hexadiene, 1,7-octadiene, 1,9- decadiene, 1,19-eicosadiene, 1,9-octadecadiene, 6-methyl-l ,S-heptadiene,methyl-1,6-octadiene, 1 1- ethyl-1,1 l-tridecadiene.

EPDM rubbers from ethylene, propylene and 5-methyl-2-norbomene areexemplified in U.S. Pat. No. 3,093,621. Suitable norbornadiene, e.g.,2-methy1 norbornadiene, 2-ethyl norbornadiene, 2-n-heptyl norbornadieneare shown in Gladding U.S. Pat. No. 3,063,973 and bicyclo compounds suchas bicyclo (2,2,2) heptadiene-2,5 are shown in Dunlop (British) Pat. No.880,904. The use of cyclooctadiene-l,5 and other cyclodienes is shown inMontecatini (Belgium) Pat. No. 623,698. Thus these can be used in makingthe EPDM elastomer 1,4-cycloheptadiene, 1 ,4- cyclooctadiene,1,6-cyclodecadiene, 1,5- cyclododecadiene, 1,7-cyclodecadiene, 1,5 ,9

cyclododecatriene, 1-methyl1,5-cyclooctadiene.

The compounds of the present invention are normally employed in anamount of at least 0.01 percent and usually 0.1 percent to 10 percent byweight of the polymer they are intended to stabilize.

They can also be used as synergistic stabilizers with other sulfurcontaining compounds. Thus, there can be employed therewith neutralsulfur compounds having a thio linkage beta to a carbon atom having botha hydrogen atom and a carboxyl group attached thereto. Such compoundsare used in an amount of 0.01 to 10 percent, preferably 0.1 5 percent.Thus there can be used pentaerythritol tetra (mercaptoacetate), 1,1,1-trimethylolethane tri (mercaptoacetate), 1,1,1-trimethylolpropane tri(mercaptoacetate), dioleyl thiodipropionate, dilauryl thiodipropionate,other thio compounds include distearyl 3,3'-thiodipropionate,dicyclohexy1-3 3 '-thiodipropionate dicetyl-3 ,3 '-thiodipropionate,dioctyl-3 ,3 -thiodipropionate, dibenzyl-3 ,3

thiodipropionate, lauryl myristyl-3,3-thiodipropionate, diphenyl-3 ,3'-thiodipropionate di-pmethoxyphenyl-3 ,3 -thiodipropionate, didecyl-3,3 -thiodipropionate, dibenzyl-3,3-thiodipropionate, diethyl- 3 ,3-thiodipropionate, lauryl ester of 3- methylmercapto propionic acid,lauryl ester of 3- butylmercapto propionic acid, lauryl ester of 3-laurylmercapto propionic acid, phenyl ester of 3- octylmercaptopropionic acid, lauryl ester of 3- phenylmercapto propionic acid, laurylester of 3-benzylmercapto propionic acid, lauryl ester of 3-(pmethoxy)phenylmercapto propionic acid, lauryl ester of 3-cyclohexylmercaptopropionic acid, lauryl ester of 3-hydroxymethylmercapto propionic acid,myristyl ester of 3-hydroxyethylmercapto propionic acid, octyl ester of3-methoxymethylmercapto propionic acid, dilauryl ester of3-hydroxymethylmercapto propionic acid, myristyl ester of3-hydroxyethylmercapto propionic acid, octyl ester of3-methoxymethylmercapt0 propionic acid, dilauryl ester of3-carboxylmethylmercapto propionic acid, dilauryl ester of3-carboxypropylmercapto propionic acid, dilauryl-4,7-dithiasebacate,dilauryl-4,7,8,l l-tetrathiotetradecandioate, dimyristyl-4,l l-dithiatetradecandioate lauryl-3- benzothiazylmercaptopropionate.Preferably the esterifying alcohol is an alkanol having to 18 carbonatoms. Other esters of beta thiocarboxylic acids set forth in GribbinsUS. Pat. No. 2,519,744 can also be used.

Other beta thiocarboxylic acids include stearyl(1,2-dicarboethoxyethylthio) acetate, stearyl (1,2-dicarbolauryloxyethylthio) acetate or the like. Compounds of this typecan be made by addition of alkyl ester of mercaptoacetic acid to adialkyl ester of maleic acid. Similar beta thiocarboxyl compounds can beused which are made by addition of an RSH compound across the maleicester double bond and where R is alkyl, aryl, alkylcarboxyalkyl,arylcarboxyalkyl or aralkyl. Examples of such compounds aredecylthiodilauryl succinate, phenylthiodioctyl succinate, cetyl l,Z-dicarboethoxyethylthio) propionate and benzylthiodimyristylsuccinate.

Similarly useful beta thiocarboxyl synergistic compounds can be preparedby addition of the RSH (mercaptan) compounds as defined above across thedouble bond of dialkyl itaconates, citraconates, fumarates or trialkylaconitates, e.g., the addition product of lauryl mercaptan with dibutylitaconate, the addition product of the stearyl ester of mercaptoaceticacid with dilauryl itaconate, the addition product of butyl mercaptanwith dilauryl citraconate, the addition product of lauryl mercaptan withtributyl aconitate, the addition product of the lauryl ester ofmercaptopropionic acid with triethyl aconitate.

The thermal stability of the polypropylene and other monoolefin polymeris adversely affected by impurities including residual catalyst. Whenthermal stability is important in addition to oxidative stability it hasbeen found valuable to include polyvalent metal salts of fatty acids inan amount of 001-10 percent preferably 0.1-5 percent, in the monoolefinpolymer formulations. Examples of such salts are calcium stearate,calcium 2- ethylhexoate, calcium octate, calcium oleate, calciumricinoleate, calcium myristate, calcium palmitate, calcium laurate,barium laurate, barium stearate, magenesium stearate as well as zincstearate, cadmium laurate, cadmium octoate, cadmium stearate and theother polyvalent metal salts of fatty acids set forth previously.

There can also be added other phenolic antioxidants in an amount of001-10 percent, preferably 0.1-5 percent. Examples of such phenolsinclude 2,6-di-t-butylp-cresol, butylated hydroxyanisole, propylgallate, 4,4- thiobis(6-t-butyl-m-cresol), 4,4-cyclohexylidene diphenol,2,5-di-t-amyl hydroquinone, 4,4'-butylidene bis( 6-t-butyl-m-cresol),hydroquinone monobenzyl ether,2,2'-methylene-bis(4-methyl-6-t-butylphenol),2,6-butyl-4-decyloxyphenol, 2-t-butyl-4- dodecyloxyphenol,2-t-butyl-4-dodecyloxyphenol, 2-tbutyl-4-octadecyloxyphenol,4,4'-methylene-bis(2,6- di-t-butylphenol), p-aminophenol,N-lauryloxy-paminophenol, 4,4'-thiobis( 3'-methyl-6-t-butyl-phenol),bis[o-( 1 l ,3 ,3-tetramethylbutyl)phenol] sulfide,4-acetyl-B-resorcylic acid, A stage p-t-butylphenolformaldehyde resin,4-dodecyloxy-2- hydroxybenzophenone, 3-hydroxy-4-(phenylcarbonyl)phenylpalmitate, n-dodecyl ester of 3-hydroxy-4-(phenylcarbonyl) phenoxyaceticacid,

and t-butylphenol as well as those shown in Belgian Pat. No. 710,873 andFrench Pat. No. 1,536,020.

The use of epoxy compounds in an amount of 0.015 percent in the polymercompositions is also valuable. Examples of such epoxy compounds includeepoxidized soya bean oil, epoxidized lard oil, epoxidized olive oil,epoxidized linseed oil, epoxidized castor oil, epoxidized peanut oil,epoxidized corn oil, epoxidized tung oil, epoxidized cottonseed oil,epichlorhydrinbisphenol A resins (epichlorhydrindiphenylolpropaneresins), phenoxy-propylene oxide, butoxypropylene oxide, epoxidizedneopentylene oleate, glycidyl epoxystearate, epoxidized a-olefins,epoxidized glycidyl soyate, dicyclopentadiene dioxide, epoxidized butyltallate, styrene oxide, dipentene dioxide, glycidol, vinyl cyclohexenedioxide, glycidyl ether of resorcinol, glycidyl ether of hydroquinone,glycidyl ether of l,5-dihydroxynaphthalene, epoxidized linseed oil fattyacids, allyl glycidyl ether, butyl glycidyl ether, cyclohexene oxide,4(2,3-epoxypropoxy) acetophenone, mesityl oxide epoxide,2-ethyl-3-propyl glycidamide, glycidyl ethers of glycerine,pentaerythritol and sorbitol, and 3,4- epoxycyclohexane-l l -dimethanolbis-9,10- epoxystearate.

The compounds of the present invention can also be employed inconjunction with phosphites and thiophosphites as antioxidants andstabilizers. The phosphite or thiophosphite is employed in an amount of0.01 to 10 percent of the polymer (or other material) being stabilized.Thus there can be employed tristearyl phosphite, trilauryltrithiophosphites in Friedman US. Pat. No. 3,039,993, Friedman US. Pat.No. 3,047,608, Friedman US. Pat. No. 3,053,878 or Larrison US. Pat. No.3,341,629.

The novel compounds of the present invention are also useful asantioxidants in an amount of 0.01 to 10 percent to stabilize foodagainst rancidity including edible animal and vegetable oils and fats,e.g., lard, soybean oil, hydrogenated cottonseed oil, coconut oil,butter, corn oil, olive oil, cod liver oil, and other fish oils, icecream, mayonnaise, pastries, cakes, breads, doughnuts, popcorn, cookies,potato chips, oleomargarine, bacon and other meats, peanuts and othernuts.

Furthermore the novel compounds of the present invention are useful asantioxidants in an amount of 0.01 to 10 percent in synthetic lubricants,polyurethanes,

polyamides, e.g., nylon 66, polyesters, e.g., polyethyleneterephthalate, polymethyl methacrylate, polyoxymethylene polymers (e.g.,Delrin and Celcon), polyphenylene oxide, polystyrene, polyacrylonitrile,styrene polymers, highly fluorinated hydrocarbons, silicones, aliphaticesters as well as any of other materials stabilized by the phenolicantioxidants of Belgian Pat. No. 710,873 or French Pat. No. 1,536,020.

PREPARATION OF INTERMEDIATES A.N,N-dimethyl-3,5-di-t-butyl-4-hydroxybenzyl amine A mixture of 103 gramsof 2,6-di-t-butylphenol, 500 ml. of ethanol, 248 grams of 25 percentaqueous solution of dimethyl amine and 75 grams of a 37 percent aqueoussolution of formaldehyde was stirred at 2 C. for 1 hour and then warmedto reflux for 4 hours. The batch was then poured onto 2 liters of coldwater- /ice and the resultant solids filtered off and washed copiouslywith water to yield 97 /2 percent of theory of the title compound, M.P.90-92 C. B. Methylene bis(butyl-3-thiopropoxycarbopropionate) A mixtureof 184.2 grams of diallyl malonate, 324.5 grams of butylmercaptopropionate, and 0.1 gram of benzophenone was irradiated withultra violet light at 40-60 C. until test for unreacted SH (by iodinetitration) was negative. Yield: quantitative, as a pale yellow oil n1.4829.

EXAMPLE 1 2,6-di-t-butyl-4-[ethylenebis(butyl-3-thiopropoxycarbopropionate)] phenol JHz-C II(C OOCHzCIIzCII; S CIInClIzC O O C 11 was then worked up by washing withwater and dilute hydrochloric acid and the organic layer solventstripped to yield the title compound in an amount of 61 parts (84percent) as a viscous amber oil, n 1.5088.

EXAMPLE 2 l-( 3 ,5-di-t-butyl-4-hydroxyphenyl)-3 ,3-bis (dodecox- Anamber liquid was prepared by refluxing 27.6 parts of1-(3,5-di-t-butyl-4-hydroxyphenyl)-3-butanone and 54.8 parts of laurylmercaptopropionate in 150 parts of toluene using 1 part ofp-toluenesulfonic acid (P.T.S.A.) as a catalyst until the theoreticalamount of water was removed. The product was then worked up as inexample 1 to yield 77 parts percent yield) of the title compound as aviscous amber oil, n 1.4983.

EXAMPLE 3 1-( 3 ,5-di-t-butyl-4-hydroxyphenyl )-3 ,3-bis(octadecoxycarboethylthio) butane (CHQA (cHsh S CH CHzC O O C nHarCHgCHz The procedure of example 2 was repeated using 71.6 parts ofstearyl mercaptopropionate in place of the lauryl mercaptopropionate toproduce the title compound in a yield of 90.8 parts (93.3 percent) as ayellow liquid, n 1.4902.

EXAMPLE 4 Bis( 3 ,5-di-t-butyl-4-hydroxybenzyl)(butoxycarboethylthiopropyl) malonate 12.4 parts of diallylbis(3,5-di-t-butyl-4- hydroxybenzyl) malonate and 6.5 parts of butylmerbis $(CHQ3 C (CHala H0 I -0H i1 1 (on )3c-' "-cm CH2 -c (can:

captopropionate were reacted in parts of hexane at reflux using 0.0004mole azoisobutyronitrile (AIBN) as the catalyst and the solvent removedby distillation. The title product was obtained in a yield of 18.7 parts(99 percent) as an amber liquid.

EXAMPLE 5 bis( 3 ,5-di-t-butyl-4-hydroxybenzyl) bis 15 16(methoxycarboethylthiopropyl) malonate There were reacted 0.22 mole of3,5-di-t-butyl-4- C(CH3)3 B)a CHaO O C CII2CH2SCII2CII2CII2O O C C O OClIzCIIzCIIzSCIIzCHzC O CH3 31 parts of I diallyl bis(3,5-di-t-butyl-4-hydroxybenzylcarboxyethyl sulfide with 0.95 mole of hydroxybenzyl)malonate and 12 parts of methyl merallyl alcohol using 0.006 mole ofP.T.S.A. as a catalyst. captopropionate were reacted under the samecondi- After removal of the excess allyl alcohol by distillation, tionsas example 4 (100 parts hexane solvent and 1 part the title compound wasrecovered in a yield of 98 per- AIBN) and there was recovered the titlecompound in cent as a colorless oil, n 1.5257.

a yield of 42.6 parts (99 percent) as a light yellow oil, 15289' 3 5 d'b 14 h d Z l 3 I 1 b h 1 i-tuty y roxy enzy aury car oxyet y EXAMPLE 62O sulfide 2 ,3-bis( dodecoxycarboethylthio) propyl-3-( 3 ,5-di-tbutyl-4-hydroxyphenyl) propionate (CHmC (CHm 0 crcrrm 25 I K (III)CHZSC IIZCIIQC 0 0 21125 CH2 S CHzCHzC O O C 12I'Izs 110-2-crr,crnoocmcnsomcmo00 21125 3 ,5-di-t-butyl-4-hydroxybenzyl mercaptan(O. 1

(0113): mole) was reacted with 0.1 mole of lauryl acrylate in 100 ml. ofbenzene at reflux using 0.5 gram of sodium methoxide as a catalyst. Thetitle compound was recov- 159 parts of 3113/1343 4 hydroxyphenyl) eredin a yield of 98 percent as a yellow oil, n 1.5025

propionate and 27.3 parts of dilauryl dithiopropionate EXAMPLE 10 werereacted for 24 hours in the presence of 0.2 part 3(butoxycarboethylthio) I of iodine as a catalyst and worked up bywashing with hydroxybenzylthio) propionate water and stripping thesolvent to yield the title compound in a yield of 40.3 parts (93percent) as a light blHilll colored oil, n 1.4885.

HO CH3 s cmcmc 0 o CIIzCHzCH; s CI'IzCHzCOOCrHg EXAMPLE 7 40 (C s)s2,2-b1s[3-(dodecoxycarboethylthlo) propoxymethyl]butyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate 36.5 parts ofallyl-3(3,5-di-t-butyl-4-hydroxy- 47.4 parts of 2,2-bis(a1lyloxymethyl)butyl-3'-(3,5- benzylthio) propionate and 16.2 parts of butylmercapdi-t-butyl-4-hydroxyphenyl) propionate and 54.8 parts topropionatewere reacted for several days in 200 parts of lauryl mercaptopropionatewere reacted several of refluxing hexane using 0.5 parts of AIBN as thecatadays u nder ultraviolet irradiation to yi'fitfii'pErfg lyst. Uponremoval of the solvent there was recovered (97 percent) of the titlecompound as a light colored the title compound as a liquid in an amountof 52.3

oil, "1725 1.4912. parts (99 percent), u 1.5188.

Alternatively the reaction can be carried out in 200 parts of hexane atreflux using 1 part AIBN as the cata- 6o EXAMPLE 1 1 lyst.

bis[ 3-(dodecyloxycarboethylthio propyl ]-a-( 3 ,5-di-t- EXAMPLE 8butyl-4-hydroxyphenyl) succinate Allyl-3 3 ,5 -di-t-butyl-4-hydroxybenzylthio )propion- C O O CHgClIgCHg S CIIQCIIQOOOC 121125 A mixture of40.56 parts of diallyl a- (3,5-di-t-butyl- 4-hydroxyphenyl) succinate,54.8 parts of lauryl mercaptopropionate and 0.5 parts of benzophenone(catalyst) was irradiated with ultra voilet light at 40-60 C. until thereaction was complete as ascertained by titration of the mixture withiodine solution. The title compound was produced in a quantitative yieldas a pale yellow oil, n 1.4938.

EXAMPLE 12 3-(dodecyloxycarboethylthio) butyl-4-hydroxyphenyl)propionate propyl-3'-(3,5-di-t- H O CH;CH;C O CHzCHaCHz S CHgCHzC 00 C2112 EXAMPLE l3 Bis( carbododecoxyethylthio)-4-hydroxy-3,5-di-tbutylphenyl methane C (CH3):

0.064 mole of 3,5di-t-butyl-4hydroxybenzaldehyde was reacted with 0.128mole of lauryl mercaptopropionate using 0.002 mole of P.T.S.A. ascatalyst. The yield of the title compound was 83 percent as a whitesolid, M.P. 34 C. 4

EXAMPLE 14 3,5-di-tbutyl-4-hydroxybenzal methylene bis (methyl-2-methyl-3thioethoxycarbopropionate) K J V or Uh.

A mixture of 23.4 grams of 3,5-di-t-butyl-4- hydroxybenzaldehyde, 42.4grams of methylene bis(methyl-Z-methyl-3thioethoxycarbopropionate), 1 .1grams of piperidine benzoate (as catalyst) and 200 ml. of anhydroustoluene was refluxed until the theoretical amount of water hadazeotroped off. The residue was washed with water, dilute hydrochloricacid solution, dilute sodium bicarbonate solution and then again withwater. After drying over sodium sulfate and filtering, the organic phasewas freed of solvents by vacuum stripping to yield the title compound ina yield of 99 percent as a viscous red oil which crystallized slowly onprolonged standing.

EXAMPLE 15 3,5di-t-butyl-4-hydroxybenzylmethylene bis (methyl-2-methyl-3thioethoxycarbopropionate) a (CHQJC ,C(CH:1:

CH: CH1CH C 0 OCHICHI S CHIOHCO OCH: 2

A mixture of 42.4 grams of methylene bis(methyl-2-methyl-3thioethoxycarbopropionate), 25.48 grams of3,5-dit-butyl-4-hydroxybenzyl chloride, 5.4 grams of sodium methoxide,and 200 ml. of benzene was stirred at room temperature overnight, theby-product filtered off and the residue worked up (solvent removed byvacuum stripping) to yield the title compound in an amount of percent oftheory as a red viscous oil, n 1.5160.

EXAMPLE 16 3,5 di-t-butyl-4-hydroxybenzylbutylcarboxyethylthiopropylcarboxymethyl ether M C I-Ia):

CHzO CH C O O cHnCHqCHg S CHQCHQCOOCIHI 0.1 mole of4-hydroxy-3,5-di-t-butyl benzyl chloride was reacted with 0.1 mole ofallyl glycolate in the presence of.0.1 mole of triethylamine in 100 ml.of benzene. After refluxing for 3 hours, the theoretical amount oftriethylamine hydrochloride was filtered off. After stripping thesolvent, the residual oil was reacted with 0.1 mole ofbutyl-3mercaptopropionate in 100 ml. hexane under reflux with 0.01 gramazobisisobutyronitrile as a catalyst. The title compound was isolated asa pale yellow oil.

EXAMPLE l7 3,5di-t-butyl-4-hydroxybenzyl laurylcarboxyethylthiopropylcarboxyethyl sulfide CIJH H: S CHaCI-Iz C O OCHzCHzCH S CHzCHz C 00 C H15 0.1 mole of3,S-di-t-butyl4hydroxybenzylallylcarboxyethyl sulfide was reacted with0.1 mole of lauryl mercaptopropionate in hexane under reflux with 0.01gram of AIBN as a catalyst. The title compound was a light colored oilsoluble in hydrocarbons but insoluble in lower alcohols, n 1.5248.

EXAMPLE l8 3,5-di-t-butyl-4-hydroxybenzyllaurylcarboxyethylthioethylcarboxyethyl ether MOH ( JH O CHzCHgO O CCHZCH: S CHzCHzCOOC 121125 0.2 mole of hydroxyethyl acrylate was reactedwith 0.2 mole of 3,5-di-t-buty1-4-hydroxbenzy1 chloride in 200 ml. ofbenzene in the presence of 0.2 mole of pyridine for 2 hours at reflux.The mixture was then drowned in 0.5 liter of water, separated from thewater and the organic solvent removed by stripping. The acrylate esterleft as a residue was then reacted with 0.2 mole of laurylmercaptopropionate in 200 ml. of t-butyl alcohol with 0.5 gram of sodiumt-butylate as a catalyst. After reacting at room temperature for 5 hoursthe mixture was again drowned in 1 liter of water. The title compoundwas isolated as a yellow oil after stripping at 100 C. and 1 mm.

The products of the invention were tested as stabilizers forpolypropylene in accelerated aging tests run at 150 C. in a circulatingair oven using the indicated amounts of the compounds per hundred partsof polypropylene (phr).

phr Hours to Degrade PPPPPPPPPPPPP UILII'JIIIIMIJIl-AmLII'JIUIIIIUIUILATEX ADHESIVES 1. Natural Rubber The effectiveness of variousantioxidants (1.0 percent concentration) in preventing discoloration andloss of flexibility of a natural rubber latex (Formulation 1 wasdetermined by applying a -mil wet film on unsized cotton and aging at100 C. for l hours. Results are shown in Table l, in order of decreasingeffectiveness.

TABLE 1 Natural Rubber Latex l 15 hours at C.

Color Flexibility Compound of Example 1 light yellow excellentAntioxidant B light yellow excellent Compound a light yellow excellentAntioxidant A light yellow excellent Antioxidant D light yellowexcellent Compound b yellow; spotting good Antioxidant C yellow;spotting good BHT brown very poor Control dark brown very poor 11.Carboxylated Styrene-butadiene Latex The effectiveness of variousantioxidants (1.0 percent concentration) in preventing discoloration andloss of flexibility of a carboxylated SBR latex (F ormulation 2) wasdetermined by preparing a free film (20 mil wet film thickness cured at45C for 30 min.), aging at C for 1 10 hours, and evaluatingdiscoloration and loss of flexibility. The results of this evaluationare listed in Table 2, in order of decreasing effectiveness.

The stability to discoloration by gas fading of various antioxidants inthe carboxylated SBR latex formulation (10 mil. wet film on unsizedcotton cloth) is shown in Table 3. All samples were white prior toexposure.

TABLE 2 Carboxylated SBR Latex Color Flexibility Compound of Example 3light yellow good Compound b light yellow good Compound a light yellowgood Antioxidant D yellow good Antioxidant B yellow good Antioxidant Clight brown poor BHT dark brown very poor Antioxidant A dark brown verypoor Control dark brown very poor TABLE 3 GAS FADE STABILITYCarboxylated SBR Latex 1 Cycle AATCC Gas Chamber 1.0% ANTlOXlDANTAntioxidant Color After Exposure Compound a White Compound of Example 3White Compound b Pale yellow Antioxidant A Bright yellow Antioxidant BBright yellow Antioxidant C Brown Antioxidant D White BHT White mined byheating at 395 F in tin cans and measuring the time to skinning. Resultsare shown in Table 4.

TABLE 4 Stabilization of Polyamide Hot Melt Adhesives AntioxidantVersamid 741 Versalon 1055 hoursat395"F. 12345678 12345678 Control01112222 00001222 Compounda 00000111 00000000 Compoundof 0000000000000011 example4 Compoundof 00000000 00000111 exampleZ Compoundb00111222 00111112 AntioxidantA 00001122 00000122 AntioxidantB 0112222201222222 AntioxidantC 00000001 01111222 Bl-lT 01111122 00111112 noskinning 1 slight local skinning 2 skinning over total surface Theformulations used in the above tests were as follows:

FORMULATION 1 Natural Rubber Latex Formulation Parts by weightCentrifuged natural rubber latex (62%) 161 KOl-l solution (10%) 5Ammonium caseinate solution 5 Zinc oxide dispersion (60%) 5 Rayoxdispersion (70%) 11 Sulfur dispersion (68%) l Setsit 51*(dithiocarbamate latex accelerator) 1 'R. T. Vanderbilt CompanyFORMULATION 2 Carboxylated SBR Latex Carboxylated SBR latex (Tylac 3010,lntemational 100.0 Latex), 49% solids; styrene/butadiene ratio (46/54)Calcium carbonate 136.0 Acrysol GS (sodium polyacrylate) 1.3 Tetrasodiumpyrophosphate (5% solution) 5.2

FORMULATION 3 (R14) HOR (1H CIhCOORz wherein R is I( nH2n) s ($nH2n R15where, R is COOR R is hydrogen or lower alkyl, n is l or 2, y is 1,where l-lOR is where R is alkyl, cycloalkyl or benzyl, R is hydrogen,alkyl, cycloalkyl or benzyl, the total carbon atoms in R and R isbetween four and 36 carbon atoms, R is alkyl or alkenyl of up to 18carbon atoms, benzyl, phenyl, tolyl or cyclohexyl.

2. A compound according to claim 1 which is bis [3-(dodecyloxycarboethylthiopropyl) ]-a- (3 ,5 -cli-t-butyl-4-hydroxypheny1) succinate.

2. A compound according to claim 1 which is bis(3-(dodecyloxycarboethylthiopropyl))- Alpha -(3,5-di-t-butyl-4-hydroxyphenyl) succinate.